CN1943060A - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

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Publication number
CN1943060A
CN1943060A CNA2006800000448A CN200680000044A CN1943060A CN 1943060 A CN1943060 A CN 1943060A CN A2006800000448 A CNA2006800000448 A CN A2006800000448A CN 200680000044 A CN200680000044 A CN 200680000044A CN 1943060 A CN1943060 A CN 1943060A
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China
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active material
discharge
battery
nonaqueous electrolytic
rechargeable nonaqueous
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CN100583500C (en
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村冈芳幸
中嶋琢也
神月清美
永山雅敏
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A non-aqueous electrolyte secondary battery comprising an anode using as an active material compound oxides capable of occluding/releasing lithium ions, a cathode, a separator, and an electrolyte consisting of a non-aqueous solvent. The discharge curve at constant-output discharging of this battery has at least two step-form inflexion points in a region ranging from 5% to 20% of a discharge capacity at a discharging terminal obtained during a period between a discharging start voltage in a fully charged state and a discharging end voltage.

Description

Rechargeable nonaqueous electrolytic battery
Technical field
The present invention relates to can be with the rechargeable nonaqueous electrolytic battery of heavy-current discharge, high power capacity and cell excellent in cycle characteristics.
Background technology
Rechargeable nonaqueous electrolytic battery owing to can access high-energy-density under high voltage, in recent years, is used as mobile communication equipment, carries the main power source of mobile device such as electronic equipment.In addition, in recent years, at the DCization demand that automobile carries usefulness or large-scale instrument, requiring to have can be with the light weight of heavy-current discharge, small-sized rechargeable nonaqueous electrolytic battery.
At these demands, because the D.C. resistance of rechargeable nonaqueous electrolytic battery inside is bigger, when carrying out heavy-current discharge, Jiao Erre increases makes the temperature of battery rise.Usually the nonaqueous solvents of employed electrolyte in rechargeable nonaqueous electrolytic battery contains the composition that seethes with excitement or decompose when surpassing about 90 ℃.Therefore, carry out battery temperature repeatedly and surpass 90 ℃ circulation time in discharging and recharging, charge/discharge capacity can sharply reduce.At such problem, launching a large amount of research.
The internal resistance of battery can be divided into the reaction resistance relevant with cell reaction, from the resistance and the current collection resistance of electrolyte and barrier film.In order to reduce current collection resistance wherein, for example open and disclose in the flat 11-233148 communique that research is anodal the spy, negative pole and outside adorn the structure of the connecting portion between part to reduce the work of battery D.C. resistance.This work is purpose with the Jiao Erre that suppresses battery.Power (output) is the long-pending of electric current and voltage.Therefore, in such the passing through permanent power discharge and will obtain in the high-power equipment of electric tool, in the situation that discharge voltage in latter stage sharply descends, it is big that discharge rate (discharging current) becomes.Because the voltage in discharge latter stage descends and to result from positive electrode, the trial of above-mentioned reduction D.C. resistance does not produce direct effect to this situation.
And, for example open to disclose in the 2004-179085 communique and propose that employing is provided with temperature sensor at battery surface the spy, when battery surface temperature arrival set point is above, the scheme that control appliance stops to move.But, except electrolyte, also include the material that other at high temperature can cause heating, the positive active material that for example discharges latter stage etc. in the rechargeable nonaqueous electrolytic battery.That is, big if positive active material is discharged to the reaction thermal change that electronegative potential then produces.Therefore, in above-mentioned control, if too highly estimated the control design temperature, then battery may become superheat state.On the contrary, if underestimation the control design temperature, then discharge capacity can extreme reduce.
In addition, for example open and disclose the scheme that descends by the rapid voltage that uses the different 2 kinds of positive active materials in average discharge volt zone to suppress to discharge latter stage of proposing in the flat 9-180718 communique the spy.In the example that has used such positive active material, when as electric tool, during with heavy-current discharge, producing following problem.That is, discharging latter stage, even want to make cell voltage reach final discharging voltage by the decline of anodal current potential, but the rising that is actually by the negative pole current potential reaches final discharging voltage.Therefore, can not obtain controlling the effect of voltage, make discharge battery in latter stage be in superheat state by the discharge voltage of positive pole.For fear of this problem, need make the irreversible capacity of the irreversible capacity of side of the positive electrode, so design capacity reduces greater than negative side.
Summary of the invention
The present invention makes in view of the above problems, and its purpose is, particularly requires in the purposes of heavy-current discharge at electric tool etc., and essence ground suppresses the discharge heating in latter stage, provide can high capacity rechargeable nonaqueous electrolytic battery.The electrolyte that rechargeable nonaqueous electrolytic battery of the present invention contains positive pole, negative pole, the barrier film between positive pole and negative pole and contains nonaqueous solvents.Positive pole is can embed composite oxides with the removal lithium embedded ion as active material.Negative pole also can embed and the removal lithium embedded ion.Discharge curve during the permanent power discharge of this battery, in following zone, have 2 or more a plurality of stair-stepping flex point, described zone be from the discharge ionization voltage under the fully charged state to resulting discharge capacity the final discharging voltage in discharge 5%～20% the zone in latter stage.By making such structure, the voltage that discharges latter stage is descended slowly, the electric current increase in the latter stage of discharging simultaneously also slows down, the rechargeable nonaqueous electrolytic battery of the rapid rising of battery temperature in the time of obtaining having relaxed heavy-current discharge.In addition, in the positive pole of rechargeable nonaqueous electrolytic battery of the present invention, two or more the lithium composite xoide with different average discharge volts at least mixed and be used as active material.And the mode of adding be make the capacity of the minimum positive active material of average discharge volt be active material all 5%～20%.By making such structure, realized having the discharge curve of stepped flex point, the electric current increase of slowly discharging simultaneously latter stage in the decline of discharge voltage in latter stage also slows down.Therefore, the rechargeable nonaqueous electrolytic battery of the rapid rising of battery temperature in the time of obtaining having relaxed heavy-current discharge.
Description of drawings
Fig. 1 is the profile of the rechargeable nonaqueous electrolytic battery of form of implementation of the present invention.
Fig. 2 has represented to be accompanied by in embodiments of the invention and the comparative example discharge voltage of discharge and the figure of variation of temperature.
Symbol description
1 negative pole
The 1A collector body
1B mixture layer
The 1C lead-in wire
2 positive poles
The 2A collector body
2B mixture layer
The 2C lead-in wire
3 barrier films
4 battery cans
5 hush panel
The 5A packing ring
5B failure of current thin plate
6 insulation boards
10A, 10B, 10C, 11 flex points
Concrete form of implementation
Fig. 1 is a profile that example is a cylindrical battery of the rechargeable nonaqueous electrolytic battery of form of implementation of the present invention.In this battery, negative pole 1, positive pole 2 and the electrode body that constitutes with barrier films 3 coilings that prevent both direct contacts that falls between are accommodated in the battery can 4.In addition, the electrolyte (not shown) that contains nonaqueous solvents contain be immersed in negative pole 1, anodal 2 and barrier film 3 in.The peristome of battery can 4 closes with hush panel 5 plugs, constitutes the battery of hermetic type.
Negative pole 1 has collector body 1A, be arranged at the mixture layer 1B that contains negative electrode active material on the collector body 1A and be connected in lead-in wire 1C on the collector body 1A.As the contained active material of mixture layer 1B, can use to embed and the material with carbon element of removal lithium embedded, crystalline, noncrystalline metal oxide etc.As material with carbon element, can list the graphite-like etc. of high crystalline material with carbon element of difficult graphite voltinism material with carbon element, the crystal structure prosperity of coke or vitreous carbon etc.More specifically can list thermally decomposed carbon class, coke class (spherical coke, needle coke, petroleum coke etc.), graphite-like, vitreous carbon class, organic high molecular compound sintered body (with the material that phenolic resins, furane resins etc. burn till, carbonization forms), carbon fiber and active carbon etc. under proper temperature.Wherein, preferably use the little material of irreversible capacity, because this is consistent with aim of the present invention.
Mixture layer 1B can be by being coated on negative electrode active material and adhesive and the resulting paste of solvent on the collector body 1A, and dry and obtain.Also can in paste, add conductive agents such as carbon black as required.In addition, also can after drying, roll.As adhesive, can use common known adhesive used in this battery.Can list polyethylene, polypropylene, polytetrafluoroethylene, Kynoar, butadiene-styrene rubber etc. particularly.Collector body 1A, lead-in wire 1C can be made of metals such as copper or nickel.
Anodal 2 have collector body 2A, be arranged at the mixture layer 2B that contains positive active material on the collector body 2A and be connected in lead-in wire 2C on the collector body 2A.Mixture layer 2B can be by being coated on positive active material and adhesive and the resulting paste of solvent on the collector body 2A, and dry back and obtaining.Also can in paste, add conductive agents such as carbon black or graphite as required.In addition, also can after drying, roll.As adhesive, can use the material same with negative pole.Collector body 2A, lead-in wire 2C can be made of metals such as aluminium or stainless steel, titaniums.
Electrolyte dissolves support salt and obtains in nonaqueous solvents.For nonaqueous solvents, the ethylene carbonate that dielectric constant is higher relatively, as to be difficult for being configured negative pole 2 graphite decomposes (below be referred to as EC), methyl ethyl carbonate (below be referred to as EMC) or dimethyl carbonate (below be referred to as DMC) etc. use as main solvent.Particularly when negative pole 2 uses graphite materials, preferably use EC, also can use the compound that the hydrogen atom among the EC has been replaced with halogen atom as main solvent.In addition, though propene carbonate (below be referred to as PC) has reactivity with graphite material, but with respect to the compound that has replaced with halogen atom as the EC of main solvent or with the hydrogen atom of EC etc., by with its part with the 2nd composition solvent exchange, can obtain more good characteristic.In addition,, improve current characteristics, reduce with the reactivity of lithium metal and improve fail safe to improve conductance for the preferred low viscosity solvent of also using of nonaqueous solvents.
On the other hand, as supporting salt,, then have no particular limits, for example can use LiPF if be dissolved in nonaqueous solvents and show the lithium salts of ionic conductivity 6, LiClO 4, LiAsF 6, LiBF 4, LiB (C 6H 5) 4, LiCH 3SO 3, CF 3SO 3Li, LiCl, LiN (C nC 2n+1SO 2) 2, LiBr etc.Particularly, as supporting that salt preferably uses LiPF 6These support that salt can use a kind separately, also can two or more mix use.
As the material of battery can 4, can use iron, nickel, stainless steel, aluminium, titanium etc.To battery can 4,, also can carry out plating etc. in order to prevent to be accompanied by the electrochemical corrosion that causes by nonaqueous electrolytic solution that discharges and recharges of battery.
When making as constituted above rechargeable nonaqueous electrolytic battery, at first,, carry out stacked across the barrier film 3 that constitutes by for example microporosity polyethylene film with the banded negative pole 1 that makes as mentioned above and banded anodal 2.After this, repeatedly reel to make at length direction and obtain the spiral type electrode body.Next, with insulation board 6 be inserted into the bottom, at internal implementation in the iron battery can 4 of nickel plating, take in this electrode body.Then, for from negative pole 1 current collection, the end of lead-in wire 1C is welded on the battery can 4.Thus, with battery can 4 and negative pole 1 conducting, make the negative side terminal of rechargeable nonaqueous electrolytic battery.In addition, for from anodal 2 current collections, use thin plate 5B to be electrically connected by cutting off electric current at the end of lead-in wire 2C with hush panel 5.Failure of current cuts off electric current with thin plate 5B according to inner pressure of battery.Thus, with hush panel 5B and anodal 2 conductings, make the side of the positive electrode terminal of rechargeable nonaqueous electrolytic battery.
Then, will support salt to be dissolved in nonaqueous solvents and prepare electrolyte and inject battery can 4 inside, then hush panel 5 be inserted the peristome of battery cans 4.Then across the packing ring 5A that constitutes by the insulative resin that has been coated with encapsulant to battery can 4 ca(u)lks, make the cylinder type rechargeable nonaqueous electrolytic battery of having fixed hush panel 5 thus.
In addition, this rechargeable nonaqueous electrolytic battery preferably is provided with the relief valve device failure of current thin plate 5B that internal gas is emitted in such as mentioned above being used to when inner pressure of battery exceeds the defined value.
Secondly, the positive active material that is included among the mixture layer 2B is described.Discharge curve during the permanent power discharge of this rechargeable nonaqueous electrolytic battery, have 2 or more a plurality of stepped flex point in following zone, described zone be discharge ionization voltage from fully charged state the time between final discharging voltage resulting discharge capacity in 5%～20% the zone in discharge latter stage.Here, the implication of stair-stepping flex point is to be illustrated in the boundary point that discharge mechanism switches between 2 phases, and perhaps the descending slope at discharge voltage in latter stage becomes big point.
Such a discharge curve can be realized by positive active material is constituted in the following manner.Positive active material is with at least 2 kinds or more kinds of back obtaining of lithium composite xoide mixing with different average discharge volts.That is, anodal 2 comprise at least as i.e. the 1st active material and as i.e. the 2nd active material of the low lithium composite xoide of ratio the 1st active material average discharge volt of active material of the lithium composite xoide of active material.And the interpolation capacity of the 2nd active material is to be 5%～20% of all active materials.By such formation, can realize having the discharge curve of stepped flex point.Because reducing, such flash-over characteristic, the voltage that discharges latter stage become slow.The electric current increase of consequently discharging latter stage also becomes slowly, and the rising of the dramatic temperature of battery has obtained alleviation during heavy-current discharge.Resemble the internal temperature of the above-mentioned rechargeable nonaqueous electrolytic battery that makes like this, owing to can confirm more accurately with temperature sensor, the control when therefore discharging and recharging becomes easily, makes the long lifetime of battery become possibility.
As the combination of such active material, can consider Li 0.98CoO 2With LiMnO 2Combination or Li 0.98CoO 2With LiNi 1/3Mn 1/3Co 1/3O 2Combination etc.Here, by will be by Li xMO 2The composition A of (M is the 3d transition metal) expression is the LiMnO of 2V～3V as the 1st active material, with average discharge volt 2Make up as the 2nd active material, the voltage that discharges latter stage is descended become the slowest, and the dramatic temperature rising of battery is alleviated the most.
And then, by Li xMO 2Among the composition A of (M is the 3d transition metal) expression, preferably satisfy 0.9≤x≤0.98.When x was lower than 0.9, anodal theoretical capacity descended, and design capacity also significantly descends thereupon.In addition, when x surpassed 0.98, anodal irreversible capacity reduced, and became by the rising of negative pole current potential to reach final discharging voltage, can not get controlling by positive discharge voltage the effect of voltage, thereby was heated at discharge battery in latter stage.
In addition, preferred LiMnO 2Weight ratio be active material all 2%～20%.Work as LiMnO 2Weight ratio be lower than at 2% o'clock, in as the 3.0V～2.5V of final discharging voltage, can not be alleviated the effect that voltage sharply descends fully, consequently can generate heat at discharge battery in latter stage.In addition, work as LiMnO 2Weight ratio surpass at 20% o'clock owing to be accompanied by LiMnO 2Increase, the discharge average voltage decline become significantly, can not obtain sufficient energy density.In addition, under with the situation of deciding power discharge, be accompanied by the decline of discharge average voltage, discharging current increases.Consequent Jiao Erre increases, thereby battery is heated.Using except that LiMnO 2Material in addition is during as the minimum active material of average discharge volt, and this preferred addition is also identical.
And one of them of preferred composition A is Li xNi yMn zCo 1-y-zO 2(0.9≤x≤0.98,0.3≤y≤0.4,0.3≤z≤0.4) or Li xNi yAl zCo L-y-zO 2(0.5≤x≤0.85,0.15≤y≤0.3,0.04≤z≤0.17).Perhaps also can mix both uses.By using such material as composition A, the discharge voltage that discharges latter stage is descended slow down, alleviate the battery heating that is accompanied by the rapid rising of electric current and produces.
In addition, nonaqueous electrolyte battery of the present invention is not limited to as above-mentioned use nonaqueous electrolytic solution as electrolytical rechargeable nonaqueous electrolytic battery, also can use gelatinous electrolyte as electrolyte.And rechargeable nonaqueous electrolytic battery of the present invention is cylinder type, square, Coin shape, and button type etc. have no particular limits for its shape, also can be size arbitrarily such as slim, large-scale in addition.
Below, in the rechargeable nonaqueous electrolytic battery to the invention process form, the embodiment that has changed the material composition of anodal active material is described in detail.
Embodiment
Embodiment 1
As positive active material, use powder 90 weight portions of following composition A and powder 10 weight portions of composition B.To composition A, use Li 2CO 3With Co 3O 4Mix to be incorporated in and burn till 10 hours resulting Li under 900 ℃ 0.95CoO 2To composition B, use Li 2CO 3, Co 3O 4, NiO and MnO 2Mix to be incorporated in and burn till 10 hours resulting Li under 900 ℃ 0.95Ni 0.35Mn 0.35Co 0.3O 2These active materials are added up to 100 weight portions and mix as acetylene carbon black 2.5 weight portions of conductive agent and as Kynoar 4 weight portions of adhesive.Thereby being suspended in, this mixture makes the cream paste in the carboxymethyl cellulose aqueous solution.This cream is stuck with paste the two sides that is coated on as the thick aluminium foil for 0.03mm of collector body 2A, the drying calendering make thick for 0.1mm, wide for 52mm, longly be the positive pole 2 of 1800mm.
As negative electrode active material, use mesophasespherule is being carried out the material that graphitization forms (below be referred to as in the middle of phase graphite) under 2800 ℃ the high temperature.Thereby to add solid constituent be in the SBR emulsion of 1 weight % and the CMC aqueous solution that solid constituent is 1 weight % and suspend and make cream and stick with paste with it.This cream muddle is distributed in the two sides of thick Copper Foil for 0.02mm, the drying calendering make thick for 0.1mm, wide for 57mm, longly be the negative pole 1 of 1860mm.
The lead-in wire 2C of aluminum is installed on anodal 2 respectively, lead-in wire 1C made of copper is installed on negative pole 1.Then, thus across thick for 0.025mm, wide for 60mm, long be wound into helical form formation electrode body for the polyethylene system barrier film 3 of 4000mm.Being inserted into diameter is 26.0mm, high in the battery can 4 of 65mm.As electrolyte, use and in EC and EMC and solvent that DMC mixes with 10: 10: 80 volume ratio, dissolved concentration and be 1.25mol/dm 3LiPF 6The solution that forms.This electrolyte is injected in battery can 4, temperature sensor is set and seals, make obtaining the battery that nominal capacity is 2.5Ah at the central part of inside battery.With the battery of this battery as embodiment 1.
Embodiment 2
As positive active material, use powder 90 weight portions of following composition A and powder 10 weight portions of composition B.To composition A, use Li 2CO 3With Co 3O 4Mix to be incorporated in and burn till 10 hours resulting Li under 900 ℃ 0.95CoO 2To composition B, use Li 2CO 3, Co 3O 4, NiO and Al 3O 4Mix to be incorporated in and burn till 10 hours resulting Li under 900 ℃ 0.95Ni 0.55Co 0.30Al 0.15O 2In addition, use the method identical to make battery with embodiment 1.With the battery of this battery as embodiment 2.
Embodiment 3
Use powder 90 weight portions of following composition A and powder 10 weight portions of composition B as positive active material.To composition A, use Li 2CO 3With Co 3O 4Mix to be incorporated in and burn till 10 hours resulting Li under 900 ℃ 0.95CoO 2To composition B, use LiMnO 2LiMnO 2Be with lithium hydroxide (LiOHH 2O) and manganite (manganite, γ-MnOOH) temperature be 99 ℃ or above, humidity reach 17.05 or the steam-laden air atmosphere of above (kg-steam/kg-dry air) in obtain after placing 3 hours, in addition, use the method identical to make battery with embodiment 1.With this battery as
The battery of embodiment 3.
Embodiment 4～6
Except the composition A with embodiment 3 changes Li respectively into 0.85CoO 2, Li 0.90CoO 2, and Li 0.98CoO 2In addition, use the method identical to make battery with embodiment 3.With the battery of these batteries as embodiment 4～6.
Embodiment 7～9
Except the weight portion with composition A among the embodiment 3: LiMnO 2Weight portion made into 98: 2,95: 5,80: 20 beyond, use the method identical to make battery with embodiment 3.With the battery of these batteries as embodiment 7～9.
Embodiment 10,11
In embodiment 3, use Li respectively as composition A 0.95Ni 0.35Mn 0.35Co 0.3O 2And Li 0.95Ni 0.40Mn 0.40Co 0.20O 2These materials are with Li 2CO 3, Co 3O 4, NiO and MnO 2Change to mix after the proportioning and be incorporated in 900 ℃ and burn till and obtained in 10 hours.In addition, use the method identical to make battery, with the battery of these batteries as embodiment 10,11 with embodiment 3.
Embodiment 12,13
In embodiment 3, use Li respectively as composition A 0.95Ni 0.80Co 0.15Al 0.05O 2And Li 0.95Ni 0.55Co 0.30Al 0.15O 2These materials are with Li 2CO 3, Co 3O 4, NiO and Al 3O 4Change to mix after the proportioning and be incorporated in 900 ℃ and burn till and obtained in 10 hours.In addition, use the method identical with embodiment 3 to make battery, these batteries are as the battery of embodiment 12,13.
Comparative example 1
In embodiment 3, as positive active material, only using composition A is Li 0.95CoO 2, use the method identical to make battery, with this battery battery of 1 as a comparative example with embodiment 3.
Comparative example 2
In embodiment 3,, only use LiMnO as positive active material 2, use the method identical to make battery, with this battery battery of 2 as a comparative example with embodiment 3.
Comparative example 3
In embodiment 3, use LiCoO 2As composition A, use the method identical to make battery, with this battery battery of 3 as a comparative example with embodiment 3.
The specification of above-mentioned prepared each battery, the evaluation result that produces by following evaluation are shown in table 1.In table 1 synthetic display the comment result who implements as follows to battery behavior.
Table 1
The composition of composition A The composition of composition B The addition of composition B (weight portion) 100W discharge capacity (%) Be up to Da Wendu (℃) Capacity sustainment rate (%) Knee voltage during discharge (V)
Embodiment 1 Li 0.95CoO 2 Li 0.95Ni 0.35Mn 0.35Co 0.30O 2 10 95 75 65 3.6
Embodiment 2 Li 0.95CoO 2 Li 0.95Ni 0.55Co 0.30Al 0.15O 2 10 95 73 67 3.3
Embodiment 3 Li 0.95CoO 2 LiMnO 2 10 95 70 70 3.0
Embodiment 4 Li 0.85CoO 2 LiMnO 2 10 75 70 70 3.0
Embodiment 5 Li 0.90CoO 2 LiMnO 2 10 95 70 70 3.0
Embodiment 6 Li 0.98CoO 2 LiMnO 2 10 95 70 70 3.0
Embodiment 7 Li 0.95CoO 2 LiMnO 2 2 96 74 65 3.0
Embodiment 8 Li 0.95CoO 2 LiMnO 2 5 96 72 65 3.0
Embodiment 9 Li 0.95CoO 2 LiMnO 2 20 92 67 75 3.0
Embodiment 10 Li 0.95Ni 0.35Mn 0.35Co 0.30O 2 LiMnO 2 10 95 65 75 3.0
Embodiment 11 Li 0.95Ni 0.40Mn 0.40Co 0.20O 2 LiMnO 2 10 95 65 75 3.0
Embodiment 12 Li 0.95Ni 0.80Co 0.15Al 0.05O 2 LiMnO 2 10 95 65 75 3.0
Embodiment 13 Li 0.95Ni 0.55Co 0.30Al 0.15O 2 LiMnO 2 10 95 65 75 3.0
Comparative example 1 Li 0.95CoO 2 - 0 95 90 10 -
Comparative example 2 - LiMnO 2 100 20 35 100 -
Comparative example 3 LiCoO 2 LiMnO 2 10 95 90 10 -
At first, estimated low power discharge characteristic under high load capacity.In 20 ℃ temperature environment, to 4.2V, will stop electric current and be made as 0.26A and carry out the constant voltage charging with the constant current charge of 2.6A.Behind 20 minutes time-out, carry out constant current discharge with 0.52A until 2.0V.This is circulated as the 1st.After then adopting the condition identical to charge, suspend 20 minutes, carry out permanent power discharge with 100W to 2.0V with the 1st circulation.This is circulated as the 2nd.The maximum temperature that the 2nd cyclic discharge capacity of investigating this moment reaches after to the ratio of the 1st cyclic discharge capacity and the 2nd circulation discharge off.And investigated the bent voltage of change of the discharge voltage when the discharge of the 1st circulation.As an example, in Fig. 2, represented the discharge voltage that be accompanied by discharge and the variation of temperature of embodiment 1 with comparative example 1.
Next has estimated charge.In 20 ℃ temperature environment, under the condition identical, repeat to discharge and recharge with the 2nd circulation of estimating high-rate discharge characteristic.With such the 300th circulation with respect to the discharge capacity ratio of the 1st circulation as the capacity sustainment rate.
Shown in (table 1), in the battery of embodiment 1,2, to as the high Li of the average discharge volt of composition A 0.95CoO 2In, added composition B, i.e. the low Li of average discharge volt xNi yMn zCo L-y-zO 2, or Li xNi yAl zCo 1-y-zO 2, to compare with comparative example 1, the battery heating of discharging latter stage reduces and is long-life.In addition, compare with comparative example 2, it is big that discharge capacity becomes.
As shown in Figure 2, the discharge curve of comparative example 1, from the discharge ionization voltage under the fully charged state until resulting discharge capacity between the final discharging voltage in discharge 5%～20% the zone in latter stage, have only 1 stair-stepping flex point 11.Flex point 11 is because Li 0.95CoO 2The slope that descends in latter stage, voltage that discharged into become and cause greatly.On the other hand, the discharge curve of embodiment 1, from the discharge ionization voltage under the fully charged state until resulting discharge capacity between the final discharging voltage in discharge 5%～20% the zone in latter stage, 3 stair-stepping flex points are arranged.The 1st flex point 10A is because Li 0.95CoO 2The slope that descends in latter stage, voltage that discharged into become and cause greatly.The 2nd flex point 10B represents that discharge mechanism is from Li 0.95CoO 2Discharge switch to Li xNi yMn zCo L-y-zO 2Discharge.The 3rd flex point 10C is because Li then xNi yMn zCo 1-y-zO 2The slope that descends in latter stage, voltage that discharged into become and cause greatly.In addition, according to the average discharge volt of the low active material of average discharge volt or the relation of addition and final discharging voltage, also have the 3rd the absent variable situation of flex point 10C.Such a discharge curve, from the discharge ionization voltage under the fully charged state in 5%～20% the zone of resulting discharge capacity between the final discharging voltage in discharge latter stage, preferably have 2 or more a plurality of stair-stepping flex point.Can alleviate as shown in Figure 2 thus in the discharge temperature rising in latter stage.
Among the embodiment 3～13,, used Li as composition A xCoO 2(0.9≤x≤0.98), Li xNi yMn zCo 1-y-zO 2(0.9≤x≤0.98,0.3≤y≤0.4,0.3≤z≤0.4), Li xNi yAl zCo L-y-zO 2(0.5≤x≤0.85,0.15≤y≤0.3,0.04≤z≤0.17).In these compositions A, the interpolation average discharge volt is extremely hanged down and is the LiMnO of 2.5V～3.0V 2, make all weight ratios of itself and active material become 2%～20%.These batteries, with respect to comparative example 1, the battery heating of discharging latter stage further reduces and is long-life.In addition, with respect to comparative example 2, it is big that discharge capacity becomes.Wherein, as composition A, used Li xNi yMn zCo 1-y-zO 2The embodiment 10,11 of (0.9≤x≤0.98,0.3≤y≤0.4,0.3≤z≤0.4), and used Li xNi yAl zCo 1-y-zO 2The embodiment 12,13 of (0.5≤x≤0.85,0.15≤y≤0.3,0.04≤z≤0.17), all very good aspect the flash-over characteristic under the permanent power power of high load capacity, the charge two.
As above, according to the rechargeable nonaqueous electrolytic battery of form of implementation of the present invention, the voltage that discharges latter stage is descended slow down, the dramatic temperature that is accompanied by the battery of electric current increase rises and is also alleviated.Yet, can think that the discharge voltage of comparative example 2 is owing to crossing the low heavy-current discharge that is unwell to.In addition, can think in embodiment 4 that because the Li ratio is low excessively, it is superfluous that irreversible capacity becomes, so capacity decline, inevitable thus discharge rate rises, and the flash-over characteristic under the permanent power power of high load capacity can descend a little.And about comparative example 3, battery capacity is to make cell voltage reach final discharging voltage according to the rising by the negative pole current potential to decide, and can not get controlling by anodal 2 potential change the effect of voltage.
In addition, though the situation to permanent power discharge is illustrated in this form of implementation, under the situation of constant current owing to also can avoid making composition A to be discharged to electronegative potential, therefore can composite inhibiting A in the discharge heating in latter stage.
According to rechargeable nonaqueous electrolytic battery of the present invention, owing to suppressed the battery heating in the latter stage of high load capacity discharge, therefore be applicable to that discharging current is bigger, and the electric tool that carries out repeated charge-discharge cycles is with power supply etc.Therefore, the availability on the industry is very big.

Claims (4)

1. rechargeable nonaqueous electrolytic battery, its comprise can embed and the composite oxides of removal lithium embedded ion as the positive pole of active material, can embed and the negative pole of removal lithium embedded ion, the barrier film between described positive pole and described negative pole and the electrolyte that contains nonaqueous solvents;
Wherein, discharge curve during the permanent power discharge of described rechargeable nonaqueous electrolytic battery has 2 or more a plurality of stair-stepping flex point in following zone, described zone be discharge ionization voltage under the fully charged state between final discharging voltage resulting discharge capacity in 5%～20% the zone in discharge latter stage.
2, a kind of rechargeable nonaqueous electrolytic battery, its comprise can embed and the composite oxides of removal lithium embedded ion as the positive pole of active material, can embed and the negative pole of removal lithium embedded ion, the barrier film between described positive pole and described negative pole and the electrolyte that contains nonaqueous solvents;
Wherein, described positive pole comprises as the 1st active material of positive active material and the 2nd active material, described the 1st active material is a lithium composite xoide, described the 2nd active material is than the low lithium composite xoide of described the 1st active material average discharge volt, the capacity of described the 2nd active material that is added be described positive active material all 5%～20%.
3, rechargeable nonaqueous electrolytic battery according to claim 2, wherein, described the 1st active material is by Li xMO 2The composition A of expression, M is the 3d transition metal, and 0.9≤x≤0.98, described the 2nd active material is LiMnO 2
4, rechargeable nonaqueous electrolytic battery according to claim 3, wherein, described composition A comprises at least a following material: Li xNi yMn zCo 1-y-zO 2, wherein 0.9≤x≤0.98 and 0.3≤y≤0.4 and 0.3≤z≤0.4, perhaps Li xNi yAl zCo 1-y-zO 2, 0.9≤x≤0.98 and 0.3≤y≤0.4 and 0.3≤z≤0.4 wherein.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102055019A (en) * 2009-10-30 2011-05-11 三星Sdi株式会社 Electrolyte for lithium battery, lithium battery comprising same and method of operating battery
CN102804460A (en) * 2009-11-02 2012-11-28 巴斯瓦有限公司 Active materials for lithium-ion batteries
CN104364669A (en) * 2012-06-13 2015-02-18 株式会社Lg化学 Apparatus and method for estimating state of charge state of charge of secondary cell including mixed cathode material
US9099738B2 (en) 2008-11-03 2015-08-04 Basvah Llc Lithium secondary batteries with positive electrode compositions and their methods of manufacturing

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9099738B2 (en) 2008-11-03 2015-08-04 Basvah Llc Lithium secondary batteries with positive electrode compositions and their methods of manufacturing
CN102055019A (en) * 2009-10-30 2011-05-11 三星Sdi株式会社 Electrolyte for lithium battery, lithium battery comprising same and method of operating battery
CN102804460A (en) * 2009-11-02 2012-11-28 巴斯瓦有限公司 Active materials for lithium-ion batteries
CN104364669A (en) * 2012-06-13 2015-02-18 株式会社Lg化学 Apparatus and method for estimating state of charge state of charge of secondary cell including mixed cathode material
CN104364669B (en) * 2012-06-13 2017-02-22 株式会社Lg 化学 Apparatus and method for estimating state of charge state of charge of secondary cell including mixed cathode material
US10408886B2 (en) 2012-06-13 2019-09-10 Lg Chem, Ltd. Apparatus and method for estimating SOC of secondary battery including blended cathode material

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